Multi-purpose lignin-carbohydrate binding system

ABSTRACT

The present invention relates to a novel, dual purpose binder formulation or system. The invention also relates to a process of agglomerating dispersed particles or fines into substantially spherical and crush resistant granules. The invention further relates to a method of covering a seed and binding the seed with a material mixture beneficial for seed germination. The invention also relates to an all-in-one seed agglomerated by the dual purpose binder formulation.

BACKGROUND OF THE INVENTION

Granulation of fertilizers and other components using binders is wellknown. Binders are used to adhere fertilizers and other componentstogether into a single particle. Conventional binders do not contributeeither economical or practical value to the fertilizer formulations.Thus, it is a cost ineffective component. In some cases, the use of abinder in a fertilizer composition also results in a granular fertilizerthat is insufficiently hard and/or round. These granular fertilizersmake encapsulation with polymers or resins difficult, resulting ininconsistent slow release fertilizers.

The prior art discloses many binder systems. These binders onlycontribute to the agglomeration of dispersed fertilizer fines andparticles. Additionally, these binders constitute a significant portionof the fertilizer composition, resulting in a fertilizer with reducednutrient value. Due to these shortcomings, fertilizers usingconventional binders result in products with low commercial viability.

Thus, there is a need in the art to provide a binding system which notonly serves the purpose of agglomerating fines and particles together,but also provides some other practical use.

SUMMARY OF THE INVENTION

The objective of this invention is to provide a new binding formulationand a processing methodology for manufacture of fertilizer particlesthat overcome these limitations.

The present invention relates to a novel, dual purpose binderformulation or system. More particularly, the invention provides abinding formulation that agglomerates or binds dispersed particles orfines into a granular composition having desired properties such asincreased granule hardness or crush resistance, increased roundness orsphericity, and increased durability and uniformity. The bindingformulation also serves as an in situ chelating agent for micronutrientsand also allows for single-stage granulation processing.

In one embodiment, dispersed particles or fines is comprised of anactive agent, such as a fertilizer, are agglomerated or bound togetherwith a binder formulation comprising a lignin-based binder and acarbohydrate based binder. This combination of binders results ingranules having increased hardness or crush resistance, increasedsphericity or roundness, and increased durability. These enhanceproperties are due, in part, to the synergistic effects of combiningbinders made of lignin based materials and carbohydrates. Thus, in oneembodiment, the lignin-based material is a lignosulfonate, and thecarbohydrate is a mixture of polyols, such as a blend of monosaccharidesand disaccharides. In another embodiment, the mixture of polyols maycomprise sorbitol, maltiol, hydrogenated starch hydrolysates (“HSH”), orcombinations thereof.

In another embodiment, the invention provides a process of agglomeratingdispersed particles or fines into substantially spherical and crushresistant granules. The agglomeration process may be achieved by asingle-stage process comprising atomizing and spraying a specific ratioof lignin-based materials and carbohydrate binder, such as a polyolmixture, into an agitating bed containing particles or fines. Thissingle-stage process allows intimate mixing of the particles or fineswith the novel binder to achieve an improved granule. The process mayadditionally comprise a recycling step, where undersized granules arereintroduced into the agitating bed until the desired granule size isachieved. The ratio of lignin to carbohydrate, such as a polyol, mayvary depending on the solubility of the particles to be agglomerated.The resulting product achieves the desired properties of increasedhardness or crush resistance, increased sphericity or roundness, andincreased durability. These enhanced properties are due to thesynergistic effects of combining the novel binder formulation and thesingle-stage processing method.

In yet another embodiment, the invention provides a method of covering aseed and binding the seed with a material mixture beneficial for seedgermination. This method may be used to produce an “all-in-one” seedproduct that is capable of germination upon appropriate hydration andexposure to sufficient sunlight. The material mixture comprises a soilconditioner that allows sufficient air transport to the seed, afertilizer, and a general purpose soil enhancer. The seed and materialmixture are bound together using the binding formulation of theinvention, which comprises a specific ratio of lignin-based material anda carbohydrate binder. In one embodiment the carbohydrate binder is amixture of polyols. The combination of the lignin and polyol produces anagglomerated particle which is substantially spherical and resistant tocrushing. In addition, the agglomerated particle is a self-containedgranule capable of germinating, when properly hydrated and exposed tosufficient sunlight, without the need for additional fertilizers ormicronutrients. The resultant granule may additionally comprisemicronutrients, such as but not limited to calcium, magnesium, sulfur,boron, copper, iron, chloride, molybdenum, zinc, or combinationsthereof. In one embodiment, the seed may be grass, vegetable, or flowerseed. In one specific embodiment, the self-contained grass seed or“all-in-one” grass seed is capable of germinating grass, when properlyhydrated and exposed to sufficient sunlight, without the need foradditional mulching or fertilizers.

In yet another embodiment, the active agent included in the granules maybe a fertilizer, such as urea. It has been unexpectedly discovered thatthe novel binder formulation of the instant invention, when used inconjunction with urea produces an anti-caking effect.

In yet another embodiment, the invention provides a method ofcultivating a seed comprising the distribution of the covered seed witha material mixture beneficial for seed germination.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a schematic of a process flow diagram of the invention.

FIG. 2 depicts a graph showing the comparable release rates between thecontrolled release fertilizer granules manufactured using the dualbinder system of the invention versus reference controlled releasefertilizer granules.

FIG. 3 shows the effects of in situ chelation of micronutrients.

FIG. 4 shows the all-in-one seed using the novel binder and rice hull.

FIG. 5 shows the all-in-one seed using the novel binder and perlite.

FIG. 6 shows a graph depicting preferred particle size distributions forheavy bulk density materials.

FIG. 7 shows a graph depicting preferred particle size distributions forheavy bulk density materials.

FIG. 8 shows a graph depicting non-preferred particle size distributionsfor heavy bulk density materials.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a composition, a method of making acomposition and a method of using a composition comprising anagglomerated particle using a novel dual binder formulation or system.The binder formulation produces granules achieving desired propertiessuch as increased particle hardness, increased crush resistance,increased roundness (i.e., sphericity), and increased durability anduniformity. These granules are produced utilizing a single-stagegranulation process. The granules produced by this method may also bewater soluble.

The binder system of the invention includes a lignin or lignin-derivedmaterial and a mixture of polyols, each present at a ratio sufficient togenerate granules with the desired properties. The ratio of the ligninto polyols used in the binder system is dictated by the solubility ofthe particles or fines to be agglomerated. “Solubility” of a particle orfine used in the formulation is directly related to a formula's tendencyto form agglomerated particles or granules. The more soluble theparticle or fine, the lower the ratio of lignin to polyols. The lesssoluble the particle or fine, the higher the ratio of lignin to polyols.

Unlike conventional binders, the binding formulation does not usehazardous chemicals such as formaldehyde and other petroleum-basedproducts. The dual binder formulation or system of the invention usesnatural and renewable by-products. As such, the binder formulation doesnot include hazardous chemicals such as, but not limited to,formaldehyde, petroleum-based chemicals, carbonate, sulfate, silicatestrengthener, dextrin, maltodextrin, cyclodextrin, pectin, soy lecithin,agar, corn starch, plantain starch, pre-gelantinized starch, or sodiumstarch glycolate, nor does it include other polymer-based binders suchas, but not limited to, polyethylene (PE), polypropylene (PP), orpolyethyl glycol (PEG). The binder formulation of the invention alsodoes not include pharmaceutical binders such as, but not limited to,hydroxyl methyl cellulose, hydroxypropyl methyl cellulose, ethoxylatedstearyl alcohols, latose, polyvinylpyrrolidone, methyl cellulose,polyethylene glycol, microcrystalline cellulose, soybean oil, cottonseedoil, gelatin, or sucrose.

Lignins, which are by-products of the wood pulping process, areconverted into lignosulfonates or sulfonated lignins. Thelignosulfonates of the binder formulation contribute to granuleshardness, roundness, and uniformity. Polyols are derived fromtraditional corn syrups, and act as tackifying agents that contribute tothe speed and efficiency of the particle or fine granulation process.This reduces the need for multi-stage processes.

The novel binder formulation of the invention allows for intimate mixingof dispersed particles or fines, such as fertilizers, micronutrients,soil conditioners, inert carriers, pesticides, plant growth hormones,plant growth regulators, soil moisture enhancers, seeds, and wettingagents. By utilizing a significantly lower quantity of the novel bindingformula, the fertilizer granules produced possess increased nutritionalvalue while simultaneously increasing hardness, roundness, sphericity,and crush resistance. In one embodiment, the invention provides abinding formulation comprising less than about 15%, between 3% and 12%,or approximately 5-6% of the total weight of the agglomerated granule.

The invention further permits intimate mixing of dispersed particles orfines, such as fertilizer and micronutrients (e.g., iron) into anagglomerated granule. An added advantage of the invention is the in situchelation of micronutrients (e.g., iron sulfate and other metalsulfates) when admixed with the novel binder. This advantage allows forsingle-step granulation without the need for an added chelation step.The chelation of micronutrients, prevents oxidation, thereby optimizingthe absorption of the micronutrients by plants.

As contemplated by the invention, lignins or lignin-derived materialsare defined as materials recovered from the wood pulping process. Ligninor lignin-derived materials may include lignosulfonates and saltsthereof. The source of lignins is well known in the art and include anyconventional cellulosic material such as hardwood and softwoods.Lignosulfonates are recovered from the sulfite preparation of wood pulp.The lignosulfonates may include calcium lignosulfonate, sodiumlignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate,aluminum lignosulfonate, potassium lignosulfonate, or zinclignosulfonate. The lignin or lignosulfonate content in the bindersystem is based on the solubility of the particles or fines. In anotherembodiment, the lignin or lignosulfonate will represent about 5-6% ofthe total weight of the binding formulation.

The carbohydrate portion of the binding formulation enhances thesphericity and results in fewer process losses. The spherical nature ofgranules is measured by “sphericity,” which is defined as the degree agiven particle shape approximates a perfect sphere. The closer thefractional number is to 1.00, the more spherical the particle shape.This value is measured using an optical particle size characterizationinstrument such as the Camsizer®, marketed in the US by HoribaInstruments. Formulations that are difficult to granulate tend to adhereto equipment rather than agglomerate with the other particles or fines.This property can reduce overall granule roundness and hardness, whileincreasing the proportion of undersized granules or fines that requirerecycling back into the granulator. The addition of carbohydrates suchas polyols or ‘sugar alcohols’ to the binder solution mixturesignificantly resolves these granulation problems.

“Polyols” or “mixture of polyols” include traditional corn syrups thatundergo a catalytic hydrogenation process or other related process. Thepolyols may include a mixture of monosaccharides, disaccharides, longchain polymeric polyols, which are also known as polyglycitol syrups orHSH, or combinations thereof. The monosaccharides may include mannitol,dulcitol, iditol, or sorbitol. The disaccharides may include isomalt,lactitol, polyglycitol, or maltitol. The polyol should be formulated inthe binder solution at a rate of 5%to 75%, or 10% to 20% or 6% to 20% ofthe weight of the main binder solution solids weight, for formulationshaving solubilities greater than 10 g/100 at 20° C. The composition ofthe polyol should contain less than or equal to 15%, or may contain lessthan or equal to 10% of monosaccharides, less than or equal to 20%,preferably less than or equal to 15% of disaccharides, and greater than50%, preferably greater than 65% HSH. In one embodiment of theinvention, the polyols contain at least 15% monosaccharides, 20%disaccharides, and 65% HSH. In another embodiment, the polyols mayinclude 15% sorbitol, 20% maltitol, and 65% HSH.

The ratio of lignin or lignosulfonate to polyol may be adjusted toaccommodate a wide range particle agglomeration solubilities. Generally,particles with higher solubility (i.e., having a greater tendency toform granules), require less polyol in the granulation process. However,particles having lower solubility (i.e., having a lower tendency to formgranules), require the use of higher levels of polyols to maintainefficient granulation. Thus, in one embodiment, particles withsolubility of less than about 0.3 grams per 100 ml of water at 20° C.may have a ratio in the range of approximately 1.5:1 to about 4:1 oflignin-derived material to a mixture of polyols. In another embodiment,particles with a solubility of greater than about 10 grams per 100 ml ofwater at 20° C. may have a ratio in the range of approximately 5:1 toabout 16:1.

Table 1, below, shows the relative ratio of polyol required for a givenformulation solubility.

TABLE 1 Average Formula Ligosulfonate:HSH Pilot Plant Trial Solubilityin Water, Ratio, based Number Product Description g/100 @ 20 C. onSolids MC09-238-A Fertilizer + Soil Conditioner 10.74 10:1  MC09-196-AFertilizer + Iron 16.93 5:1 MC09-224-A Lawns Fertilizer 11.59 10:1 MC10-020-A Lawns Fertilizer 76.1 16:1  MC09-287-A All-In-One Grass Seed,Rice Hulls 0.26 3:1 MC09-294-A All-In-One Grass Seed, Rice Hulls 0.264:1 MC10-076-A All-In-One Grass Seed, Perlite 0.26 2:1 MC10-132-AAll-In-One Grass Seed, Perlite 0.26 1.5:1  

In one embodiment, the ratio of lignosulfonate to polyol is at least1.5:1. In another embodiment, the ratio of lignosulfonate to polyol iswithin the range of approximately 1.5-10:1. In yet another embodimentthe ratio of lignosulfonate to polyol may include 2:1, 3:1, 4:1, 5:1,10:1, or 16:1.

As a result of the binding formulation comprising a specific ratio oflignin and polyols, the agglomerated particles have the physicalproperty of being substantially spherical and retaining significantresistance to crushing. These physical characteristics are the directresult of the process of agglomerating the particles in combination withthe specific ratio of lignin and polyols applied to small and fine sizedparticles. The process allows for small under-size particles to berecycled back into a granulating apparatus at a rate of 2-3 times therate of freshly added particles. The recycling process aids in thegranulation process by allowing under-sized particles to graduallyaccumulation in particle size, without sacrificing granule properties.The combination of a preferred binder formula, the applicationtechniques and processing steps, such as recycle rate ratios gives riseto the above-cited desirable properties of the granules of the presentinvention.

The initial particle sizes used in the agglomeration process may vary.In one embodiment, fine or powdered sized particles are the startingmaterial. These particles can be in the size range of about 20-40 SizeGuide Number (“SGN”). In another embodiment, the SGN may range fromabout 4-10 SGN, if smoother particle surfaces are desired. Particleswhich have been agglomerated into a granule may have sphericitypercentages greater of at least 85%, more preferably 87%, 88%, 89%, 90%,91%, or 93%. The aspect ratios are greater than 0.78, more preferably,0.8, 0.83, 0.87. The agglomerated particle will also have a resistanceto crushing which is capable of exceeding approximately 2.0 Lbs. force.

Because the granules generated by the invention have greater sphericity,hardness and aspect ratios, the granules produced are more effective forpolymer or resin coatings. This allows for the production of consistentcontrolled release water soluble granule.

These properties allow granules produced by this invention to be used assubstrates for encapsulation. The coating which encapsulates the granulemay be a sulfur-based coating, a solvent-based polymer coating, orwater-based latex coating. In one embodiment, the intermediate coatingis a water-based latex coating. The latex coating can be selected frompolymeric insoluble latex materials, wherein the material comprisescopolymer blends of polyvinylidene chloride or ethylenically unsaturatedco-monomers such as methyl methacrylates, acrylonitriles, and methylacrylates, and mixtures thereof. The latex layer is capable ofcontrolling the rate of inner core release, based of the weighting andthickness of the polymeric coating. The granules may also beencapsulated with molten methylene urea resin, molten sulfur, moltenwaxes, polyurethane resins, alkyd resins, as well as other polymersystems. Solvent-based polymers that may be used in the invention aredescribed, for example, in U.S. Pat. Nos. 4,019,890 and 3,223,518, whichare incorporated herein by reference. U.S. Pat. Nos. 4,549,897 and5,186,732 provide examples of various water-based polymers coated in theabsence of solvents, and provide for a safe and cost effectivealternative, both of which are incorporated herein by reference.

The particles, particulates, or particulate matter of the invention mayinclude any material desired to be agglomerated into a pellet, cake,prill, spheroid tablet, pastille, or flake. The particle generallyrefers to the active agents bound together, with other components, toform a granular composition. These particles may include agriculturallyactive materials such as fertilizers, pesticides, soil conditioners oragents, seeds, rice hulls, acaricides, avicides, bactericides, biocides,germicides, rodenticides, vulpicides, nutrient, pesticides, herbicides,fungicides, growth regulators, insecticides, animal and insectrepellants, antibiotic, defoliants, pH adjustors, soil conditioners,molluscicides, and mixtures or combinations thereof. Additionally,particle, particulate, or particulate matter may refer to materials usedin pharmaceutical compositions such as drugs, vitamins, or othersupplements. More still, particle, particulate, or particulate mattermay refer to materials used in the preparation of food products such asbut not limited to, granulated cereals, candies, spices, nuts, andmeats. The term particle, particulate, or particulate matter willgenerally not include other components of the granular composition suchas the lignin-derived material and the mixture of polyols.

In another embodiment the particle may include a fertilizer, nutrient,pesticide, herbicide, fungicide, growth regulator, insecticide, animaland insect repellant, antibiotic, or combinations thereof. In anotherembodiment, the agricultural product is a fertilizer. In a particularembodiment, urea particles combined with the novel binder of theinvention exhibit unique anti-caking effects. The polyol component ofthe binder system provides the unexpected benefit of inhibiting cakingor clumping in urea-containing fertilizers by reducing the aspect ratiosof the crystals formed in the fertilizer, such that the levelseffectively eliminate caking in a treated fertilizer. The details ofthis benefit are outlined in U.S. Pat. No. 7,776,125, which is herebyincorporated by reference.

In yet another embodiment of the invention, the particle may alsoinclude various seeds, such as grass, vegetables, flowers, or grains.The agglomerated product may also be envisioned as an “all-in-one” seedproduct, which comprises fertilizer, soil conditioning agents,micronutrients, seed, perlite (or materials having similar open porespace in their physical composition such as synthetic expandedmaterials, coir, and diatomaceous earth), and optionally a bulk densitymaterials (e.g., limestone, calcium carbonate, calcium sulfate,dolomite, marble, powdered granite, or combinations thereof), and whichmay be subsequently encapsulated by a protective coating. This all-in-one seed product requires only the addition of water and sufficientsunlight to initiate growth.

Thus, in one embodiment, the all-in-one-seed product is a granularproduct that comprises (i) particles comprised of a viable seed, soilconditioning agents, fertilizers, micronutrients, soil moistureenhancers, oxygen enhancers, growth enhancers, hormones, and fungicides,and mixtures thereof; and(ii) a binding agent comprising a lignin and amixture of polyols in a ratio sufficient to agglomerate the particleinto a spherical and crush resistant granular product. The ratio oflignin and polyol in the binding agent will be determined by thesolubility of the various particles. In one embodiment the ratio of thelignin and the polyols in the binding agent is about 1.5:1 to about 4:1when the solubility is less than about 0.3 g/100 ml of water at 20° C.Surprisingly, the aggregation or agglomeration of fertilizer,micronutrients, grass seed, perlite (or materials having similar openpore space in their physical composition such as synthetic expandedmaterials, coir, and diatomaceous earth), into an all-in-one granuleproduct produced greater than expected results when compared to other anall-in-one grass seeds products using rice hull. In another embodiment,the addition of a bulk density material to the all-in-one granuleprovides surprisingly more granule hardness, sphericity, and germinationrates. Bulk density materials added at a volumetric ratio of perlite toheavy bulk density material in the range of about 1:1 to 4:1. In oneembodiment the ratio is 3:1 perlite to bulk density material.

The addition of a “bulk density material” provides for a final granulewith improved hardness and spreadability when used in a rotary spreaderor other broadcasting devices that distributes materials over a largerarea. The bulk density material also improves the overall efficiency inthe granulation product by providing an aide or a substrate onto whichthe agglomeration process may occur. By utilizing its weight, the bulkdensity material allows for faster agglomeration rate by helping to rollup the seed and binder into granules, thereby and enhancing theformation of a spherical shape. When added at a rate of 5-20% by weightat the appropriate particle size distribution, the ability to improvethe efficiency of agglomeration, hardness, and sphericity is achieved.

The bulk density material may be any heavy material in the range ofabout 55 to 75 Lbs/cu Ft. (e.g., 60 to 70 Lbs/cu Ft.) In one embodiment,the bulk density material is selected from limestone, calcium carbonate,calcium sulfate, dolomite, marble, powder granite or any combinationthereof.

The agglomeration rate and the formula's overall binder utilizationefficiency is a direct function of the heavy bulk density material'sparticle size distribution. If the particle size distribution of bulkdensity material is too large, significantly more binder solution isrequired to roll up spherical granules. This can increase cost of theformula, while potentially reducing product performance. Thus, in oneembodiment, the particle size distribution should have to least 99% ofthe material weight with a size less than 44 microns, with 30-70% ofthat weight having a particle size less than 5 microns, while also beinglarger than 1 micron. Using materials having larger particle sizedistribution slows down the granulation process and requires the use ofgreater amounts of binder solution. Also the use of excess binderincreases production costs. Also contemplated in the invention is aprocess of manufacturing an agglomerated particle to generate granuleswith increased crush resistance and sphericity. The process involves theatomization of a specific ratio of lignin to polyol such that the bindersolution is intimately mixed with the particles. The viscosity of thebinder solution is in the range of 10-20 cps at 25° C. The atomizationprovides an intimate mixing of components with the added benefit ofminimizing the amount of binder applied to the particles. By utilizing abinder, such as calcium lignosulfonate, and formulating a fertilizercontaining micronutrients, such as iron sulfate or other metal sulfates(e.g., zinc, manganese, copper, and magnesium), intimate mixing allowschelation of the lignosulfonate. The most effective chelation occurswhen the weight percentage of lignosulfate used in the binder solutionexceeds the weight percentage of total iron or metal by approximately70%. Less effective chelation, which may result in oxidation, begins ifthe weight percentage of lignosulfate exceeds the weight percentage ofiron or other metals by approximately 25%. As a result of theatomization, the binder solution is approximately 5-6% of the totalweight of the final granular product.

Thus, in one embodiment, the invention provides a method ofmanufacturing a granular product composition of the inventioncomprising: (i) proving particles comprised of active agents; (ii)providing a binding agent comprising a lignin or lignin-derived materialand a mixture of polyols in a ratio which is dictated by the solubilityof the particles; (iii) agitating or mixing the particles for asufficient period of time to generate a homogeneous blend; and (iv)introducing an atomized form of the binding agent through an atomizedspray for at least a portion of the time the particles are agitating ormixing. The ratio of the lignin and polyol in the binding agent willvary depending on the solubility of the particles. Thus, in oneembodiment, the ratio of the lignin to polyols in the binding agent isabout 5:1 to 16:1 when the solubility of the particles is greater thanabout 10 g/100 ml at 20° C. In another embodiment, the ratio of thelignin to polyols in the binding agent is about 1.5:1 to 4:1 when thesolubility of the particles is less than about 0.3 g/100 ml at 20° C.

In another embodiment, the method of manufacturing may also comprise adrying step. The times and temperature required for drying are dictatedby the particular particle used in the manufacturing process. Thesolubility of the particle used also plays a role in the determinationof the drying times and temperatures. In one embodiment, the dryingtimes for a particle having a solubility range of 11-80 g/100 ml at 20°C. will vary from about 10 minutes to about 20 minutes. In anotherembodiment, the temperature of drying may also be dictated by theparticular particle used in the manufacturing process. Dryingtemperatures ranging from 120° F. to about 185° F. will be desired withparticles having a solubility range of 11-80 g/100 ml at 20° C.Particles having solubility less than 1.0 g/100 ml at 20° C. may havedrying times of about 5 minutes to about 10 minutes. Drying temperaturesranging from 95° C. to about 115° C. will be desired with particleshaving solubilities of less than 1.0 g/100 ml at 20° C.

Mixing or agitation of the various particles in the manufacture of thegranular product also plays an important role in the formation of ahighly spherical and hard granular product. In order to maintain ahighly spherical particle, a mixing device, such as but not limited to adrum, fluid bed, or pan, must move at a consistent speed such that theparticles are moving in a continuous rolling motion. The continuousmotion allows the particles to pass before the binder spray nozzlesection of the mixing device, providing for even application of thebinder formulation. The speed at which the particles roll is lesscritical than maintaining overall consistent movement. If the materialsundergo intermittent motion, the relative sphericity of the granuleswill be compromised.

Another embodiment of the invention involves a method of fertilizingvegetation comprising adding a granule manufactured by the instantinvention. Such methods may include applying to vegetation a fertilizercomposition which is substantially spherical and crush resistant,comprising an agglomeration of nutrients, micronutrients,lignosulfonate, and polyols in a ratio sufficient to generate afertilizer granule which is at least about 70%-95% spherical. In oneembodiment, the fertilizer granule is about 80%-90% spherical or about87% spherical. The spherical granule is also capable of withstanding 2lbs/force when the lignin and polyols ratio is about 1.5:1 to about16:1. In another embodiment, the ratio of the lignin to polyols varydepending on the solubility of the particles used in the manufacture ofthe granule.

Another embodiment of the invention is a method of cultivating grasscomprising applying to said grass a composition comprising anagglomerated particle comprising a grass seed, perlite, nutrients, andmicronutrients, wherein the particle comprises lignosulfonate andpolyols in a ratio sufficient to form a particle that is at least 87%spherical and resistant to 2.0 lbs/force. The lignosulfonate and polyolsare in a ratio of about 1.5:1 to about 16:1, but vary depending on thesolubility of the particles used in the manufacture of the granule. Thelignosulfonate may include calcium lignosulfonate, sodiumlignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate,aluminium lignosulfonate, or combinations thereof. The polyols mayinclude monosaccharides, disaccharides, and HSH, which may compriseapproximately 15% monosaccharides, 20% disaccharides, and 65% HSH.

Compositions according to one or more embodiments of the presentinvention will be further described, and advantages thereof, will bemade apparent with reference to the following examples, which areprovided to illustrate the practice of the invention and not to limitits scope of the invention as defined by the appended claims.

EXAMPLES

(A) General Process for Preparing the Agglomerated Particles.

The granulation process is conducted at ambient temperatures andtherefore can be used for fertilizer and pesticide combinations, as wellas biological materials such as seed.

Granules of the invention initially require all materials in theformulation to be sized in powder form with an approximate size of 20-40SGN. All particle components, such as fertilizers, micronutrients,seeds, and perlite are mixed together to form a relatively uniformparticle blend. This blending process ensures that the mixture isthoroughly mixed. The particle blend is then feed into a granulatorapparatus at ambient temperature and normal humidity.

As the mixed powder blend enters the granulator, typically a horizontalrotating drum, the binder solution (i.e., lignosulfonate and polyols) isapplied at a temperature range of 110-130° F. and solution viscosity of10-20 cps. The viscosity of the binder solution allows for atomizationof the binder, thereby allowing intimate mixing with powder blend. Theatomization is achieved by using air-assist spray nozzles that willdeliver 10-25 SCFH of air per GPH of binder solution.

As the rolling action in the granulator creates round particles, the wetgranules are then conveyed to a pre-dryer, which may also be a rotatingdrum. The pre-dryer removes approximately 30-50% of the moisture addedfrom the binder solution in the granulator and operates in a temperaturerange of ambient to 135° F. The pre-dryer removes enough moisture toallow increased granules strength for screening. Undersized granules(i.e., fines) are recycled back into the granulator apparatus at 2-3times the rate of fresh powder blend. The moisture level in thegranulator apparatus is sufficient to allow effective adherence of thenext layer of binder solution and powder blend.

Granules of the appropriate size are then dried in the fluid bed drierat a temperature range of ambient to 180° F. until a final moistureconcentration 0.5-1.0% is achieved. (See FIG. 1). The finished granulescan be heated in-situ and transferred to other mechanical devices forresin coating to add controlled release coatings if desired.

(B) Various Trials Involving Different Ratios and Particles Amounts

Tables 2-7 show the material ratios loaded as powder mixes into thegranulator on a continuous basis at 50 lbs/hr. Each trial was thencompleted in the same manner as described in the previous section.

TABLE 2 Pilot Plant Run Number MC09-084-A Lbs/1000 Solids Blend RatioSolid Raw Material Feeds K2SO4 287.38 30.0% KCI 0.0% ASN 520.00 55.0% AS0.00 0.0% MAP 90.00 9.0% MnSO4 0.0% FeSO4 55.00 6.0% Total Formulasolids 952.38 Binder Solution Type Norling A + Water Solution 216.67

TABLE 3 Pilot Plant Run Number MC09-147-A Lbs/1000 Solids Blend RatioSolid Raw Material Feeds K2SO4 160.38 17.0% KCI 0.00 0.0% ASN 670.0070.4% AS 0.00 0.0% MAP 82.00 8.6% MnSO4 0.0% MicroMax Package 40.00 4.0%FeSO4 0.00 0.0% Total Formula solids 952.38 Binder Solution Type NorlingA + Water Solution 162.50

TABLE 4 Pilot Plant Run Number MC09-155-A Lbs/1000 Solids Blend RatioSolid Raw Material Feeds K2SO4 204.38 21.9%  KCI 0.00 0.0% ASN 553.0058.1%  AS 90.00 9.0% MAP 0.00 0.0% MnSO4 0.0% MicroMax Package 0.00 0.0%FeSO4 105.00 11.0%  Total Formula solids 952.38 100.00%   BinderSolution Type Norling A + Water Solution 162.50

TABLE 5 Pilot Plant Run Number MC09-168-A Lbs/1000 Solids Blend RatioSolid Raw Material Feeds K2SO4 122.38 12.8%  KCI 0.00 0.0% ASN 620.0065.1%  AS 0.00 0.0% MAP 0.00 0.0% Iron Oxide 0.00 0.0% MicroMax Package0.00 0.0% FeSO4 210.00 22.1%  Total Formula solids 952.38 100.00%  Binder Solution Type Norling A + Water Solution 162.51

TABLE 6 Pilot Plant Run Number MC09-176-A Lbs/1000 Solids Blend RatioSolid Raw Material Feeds K2SO4 207.38 22.0%  KCI 0.00 0.0% ASN 240.0025.2%  AS 0.00 0.0% MAP 405.00 42.5%  Iron Oxide 0.00 0.0% MicroMaxPackage 50.00 5.0% FeSO4 50.00 5.3% Total Formula solids 952.38100.00%   Binder Solution Type Norling A + Water Solution 172.23

TABLE 7 Pilot Plant Run Number MC09-196-A Lbs/1000 Solid Blend RatioSolid Raw Material Feeds K2SO4 203.42 22.0%  KCI 0.00 0.0% ASN 575.0060.9%  AS 60.00 6.0% MAP 0.00 0.0% Iron Oxide 0.00 0.0% MicroMax Package0.00 0.0% FeSO4 105.00 11.1%  Total Formula solids 943.42 100.00%  Binder Solution Type Norling A + Water Solution 199.39 Hystar 3375 17.33

(C) A Comparison of Various Granules Produced

This example shows the resulting physical data from materials producedusing the inventive methods described herein. The SGN is the averagesize diameter in mm times 100, the UI is the uniformity index, B/L isthe aspect ratio, SPH is the sphericity divided by 100, and the Load atRupture is the crush strength in Lbs. force. The results show that thetarget properties can all be met. However, larger concentrations ofcertain raw materials can reduce particle hardness as well assphericity.

Load At Trial Number SGN UI B/L SPH Rupture MC09-084-A 353 52.3 0.8720.933 5.666 MC09-147-A 298.9 43.1 0.829 0.917 3.139 MC09-176-A 192.548.8 0.806 0.896 2.042 MC09-196-A 238 52.1 0.784 0.871 2.313 MC09-168-A162.8 48.1 0.771 0.865 0.576 MC09-155-A 216.9 42.9 0.765 0.846 0.401

The Table below shows a heavy bulk density material (e.g., calciumcarbonate) in the preferred size range included in a formula compared toa similar formula not containing the heavy bulk density material. Theresults show on-size yield, which is an indication of agglomerationefficiency, increases, along with particle sphericity and granule crushstrength.

Heavy Wt % Bulk On-Size Crush Heavy Density Formula Run Yield, Sphe-Stength, Bulk Material Number Number Lbs. ricity Lbs. Density N/A S14021MC09-224 72.1 0.893 3.33 0.0 CaCO3 515518 MC11-026 109.3 0.910 3.40 15.0CaCO3 515518 MC11-040 106.3 0.903 4.00 15.0

(D) The Controlled Release of Granules Compared to Reference Granules

In this example, materials produced using the methods described hereinwere coated with polymer resin for controlled release and their nutrientrelease profiles compared to similar coatings using commerciallyavailable substrates. The samples noted as “Invention” are substratesproduced using methods described herein. (see FIG. 2) Samples noted as“Reference” are comparative commercially available fertilizersubstrates.

Two polymer resin systems (i.e., alkyd resin or polyurethane resin) wereshown in this example. Samples noted with “Resin Coating” were producedusing an alkyd resin coating. Samples noted with “Polymer Coating” wereproduced using a polyurethane resin coating. The testing was conductedby placing the coated materials in a container (at room temperature inwater or sand) and measuring the amounts of nitrogen released atspecific time intervals. The results demonstrate that the “Invention”samples can be used to manufacture controlled release coatings withsimilar performance to the “Reference” binding systems.

(E) The In Situ Oxidation of Micronutrients.

This example shows the non-staining effect of the fertilizer with FeSO4produced using the methods described herein. Small samples of ferroussulfate (FeSO4), a product called MicroMax, containing micro elementsulfates (e.g., iron, manganese, zinc, and copper) and a completefertilizer granule “Kemira 17-10-13”, which also contains chelated EDTAiron, were placed on a concrete block and irrigated. These samples werecompared to experimental products, designated “MC09-084-A,” which wasproduced using the inventive methods described herein. MC09-084-A wasformulated with iron sulfate (FeSO4) and irrigated in the same manner.The results show that the samples that did not have chelated ironoxidized and stained the concrete block. Samples MC09-084-A and theKemira 17-10-13 did not stain the concrete.

(F) The Addition of Bulk Density Material

To determine if the granules could be improved in terms of hardness,sphericity, and/or agglomeration, bulk density materials were added tothe granulation process.

FIGS. 6, 7 and 8 show the particle size distributions of a heavy bulkdensity material. The X-axis indicates the ASTM Mesh size measured ineach sample, while the Y-axis indicates the weight % found in each ASTMMesh size fraction. Each sizing test was replicated four times, asdisplayed with four ‘bars’ in each size fraction.

FIGS. 6 and 7 provide example particle size distributions for heavy bulkdensity materials in the preferred size range of 99% of the materialless than 44 microns and 30-70% also less than 5 microns. FIG. 8provides a heavy bulk density material with a particle size distributionwith only 40% by weight of particle with a size less than 44 microns andabout 9% less than 5 microns. This particles result in the granulationprocess requiring two times the amount of binder, compared to using thepreferred particle size of heavy bulk density material.

The Table below shows the effect of 5 micron wt % versus binder solutionutilization. This table shows that when the particle size distributionof the heavy bulk density material is similar to that displayed in FIG.8, binder requirements increase by nearly 2×.

Heavy HBD-5 Binder Granulation Bulk Micron Solution % Yield, Lbs.Density Formula Wt Solids, Ligno:HSH On-Size Per Material NumberFraction Lbs./1000 Wt. Ratio run CaCO3 62.024 69% 158 4 40.3 CaCO362.024 44% 158 4 45 CaCO3 62.024  9% 285 4 26.8

(G) The All-In-One Seed Using the Novel Binding System.

As contemplated by the invention, a single granule comprising a seed,fertilizer, soil conditioning agents, micronutrients, growth enhancer,hormones, fungicides, and perlite may be used to form an all inclusiveor all-in-one seed particle.

To test the ability of the novel binding system to enhance the growth ofa seed, an all-in-one system comprising the novel binding system of theinvention was used. The all-in-one system tested the effects of thenovel binder to grow grass in either rice hulls or perlite. The othercomponents of the all-in one seed system were kept identical with theexception of either perlite or rice hull.

Surprisingly, the all-in-one seeds comprising the novel binding systemand perlite exhibited an increase in germination when compared to theall-in-one seed comprising the binding system and rice hulls. (see FIGS.4 and 5). The combination of perlite and novel binder allowed sufficientair flow transmission to allow germination of the grass seed. Thecombination of rice hulls and novel binder did not allow sufficient airtransmission to the seed and no germination could be achieved. FIGS. 4and 5 depict this difference when attempting to germinate the granulatedseed particles in controlled greenhouse or growth chamber evaluationmethods.

(H) All-In-One Seed with Bulk Density Material

The perlite used in the all-in-one seed is a lighter material, typicallyhaving a bulk density ranging from 5-10 ls./cu. ft. It is a porous andopen structure allowing for air transmission to the seed. However, thisstructure also helps the material achieve a relatively high liquidholding capacity in the range of about 200-300% of its own weight. Theability to retain high levels of liquid helps the particle provide morewater for the new seedlings as they are growing and becomingestablished.

During the granulation process, due to its high liquid holding capacity,perlite may adsorb significant amounts of the binder solution, describedherein, potentially causing a reduction in the granulation process. Theaddition of more binder may seal off the open pores of the perlite, thusreducing its air transmission rate, resulting in a product with reduceseed germination rates.

In order to prevent the occurrence of reduced germination rates in thefinal product, bulk density materials, such as limestone, calciumcarbonate, calcium sulfate, dolomite, marble, powdered granite, orcombinations thereof were added to the production of the all-in-oneseed.

To the components of the all-in-one seed, bulk density materials wereadded at a volumetric ratio of perlite to heavy bulk density material ofabout 1:1 to 4:1. By using this ratio, the formula achieves a balancebetween granule integrity, air transmission to seed, and agglomerationor ‘roll-up’ of seeds into the granules. This balance is achieved, whilealso maintaining effective seed germination rates.

All documents presented herein (e.g., patents, patent applications,non-patent literature documents) are hereby incorporated by reference intheir entireties.

1. A granule comprising (i) particles comprising an active agent and(ii) a binding agent comprising a lignin-derived material and a mixtureof polyols, wherein the ratio of said lignin-derived material to saidmixture of polyols is sufficient to generate granules which aresubstantially spherical and/or crush resistant; and wherein the activeagent is an agriculturally active agent, a pharmaceutically activeagent, or a food product.
 2. The granule of claim 1, wherein said ratiois about 5:1 to about 20:1 when the solubility of the particle is about10 g/100 ml in water at 20° C. or in a ratio of about 1.5 to about 4:1when the solubility of the particle is about 0.3 g/100 ml in water at20° C. 3-4. (canceled)
 5. The granule of claim 1, wherein the bindingagent comprises a ratio of lignin-derived material to a mixture ofpolyols of about 5:1 to 20:1 when the solubility of the particle isgreater than 10 g/100 ml of water at 20° C., or wherein the bindingagent comprises a ratio of lignin-derived material to a mixture ofpolyols of about 1.5:1 to 4:1 when the solubility of the particulatematerial is less than 0.3 g/100 ml of water at 20° C., with the provisothat the binding agent does not comprise formaldehyde, petroleum basedchemicals, carbonate, sulfate, or silicate strengthener.
 6. (canceled)7. The granule of claim 1, wherein the active agent includesfertilizers, micronutrients, pesticides, seeds, granulated food,pharmaceutical materials, or combinations thereof. 8-10. (canceled) 11.The granule of claim 1, wherein the mixture of polyols comprises about10-20% by weight of the lignin.
 12. The granule of claim 1, wherein themixture of polyols comprises an amount of up to about 15%monosaccharides, an amount of up to about 20% disaccharides, and atleast an amount up to about 50% hydrogenated starch hydrolysates (HSH).13-18. (canceled)
 19. The granule of claim 1, wherein the agriculturallyactive agent is a fertilizer
 20. The granule of claim 19, wherein saidfertilizer comprises nitrogen, phosphorus, potassium, or combinationsthereof.
 21. The granule of claim 7, wherein said micronutrients includecalcium, magnesium, sulfur, boron, copper, iron, chloride, magnesium,molybdenum, zinc, or combinations thereof.
 22. (canceled)
 23. Thegranule of claim 1, wherein the particles and binding agent are in aneffective amount to chelate a micronutrient. 24-26. (canceled)
 27. Acrush resistant granular fertilizer comprising fertilizer particles,micronutrients, lignosulfonate, and polyols, wherein the lignosulfonateand polyols are each in a concentration capable of generating apopulation of the granules of claim 1, wherein each granule has asphericity of at least 85%, has an aspect ratio of at least 0.78, andhas a hardness of 2 lbs/force.
 28. The fertilizer of claim 27, whereinlignosulfonate and polyols are in a ratio of about 1.5:1 to about 16:1,with a solubility of 0.3 g/100 ml of water at 20° C.
 29. The fertilizerof claim 27, wherein the mixture of polyols includes 15% sorbitol, 20%maltitol, and 65% HSH. 30-31. (canceled)
 32. A binding formulationcomprising a lignin, a mixture of polyols in a ratio sufficient to forma the crush resistant and/or substantially spherical granule of claim 1,and a fertilizer wherein the fertilizer comprises nitrogen, phosphorus,potassium, micronutrients, or combinations thereof; wherein saidmicronutrients include calcium, magnesium, sulfur, boron, copper, iron,chloride, magnesium, molybdenum, zinc, or combinations thereof; whereinthe ratio of lignin to the mixture of polyols is in the range of about1.5:1 to about 16:1; wherein the crush resistance of the granule iscapable of withstanding at least 2 lbs/force; and wherein the granulehas a sphericity of at least 85%.
 33. The formulation of claim 32,wherein said lignin comprises calcium lignosulfonate, sodiumlignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate,aluminum lignosulfonate, chromium lignosulfonate, or combinationsthereof.
 34. The formulation of claim 32, wherein the mixture of polyolsincludes monosaccharides, disaccharides, HSH, or combinations thereof.35. The formulation of claim 32, wherein the mixture of polyolscomprises at least 10-20% of the dry weight of the lignin. 36-39.(canceled)
 40. A method of making spherical and crush resistant granulescomprising admixing: a. a particle; b. a lignosulfonate; and c. amixture of polyols; in a sufficient ratio to generate an agglomeratedparticle, wherein each particle is at least 85% spherical, has an aspectratio of 0.78, and is crush resistant at 2.0 lbs/force; wherein theparticle includes fertilizers, herbicides, pesticides, micronutrients,seeds, soil conditioners, inert carriers, plant growth hormones, plantgrowth regulators, soil moisture enhancers, seeds, and wetting agents orcombinations thereof; and wherein the lignosulfonate includes calciumlignosulfonate, sodium lignosulfonate, ammonium lignosulfonate,magnesium lignosulfonate, aluminum lignosulfonate, chromiumlignosulfonate or combinations thereof; wherein the mixture of polyolsincludes monosaccharides, disaccharides, HSH, or combinations thereof;and wherein the lignosulfonate and mixture of polyols is premixed into abinder solution. 41-45. (canceled)
 46. A method of preparing highlyspherical and crush resistant granules comprising the steps of: d.admixing particulate material to form a homogeneous blend, wherein theparticulate materials are herbicides, pesticides, micronutrients, seeds,or combinations thereof; e. incorporating at ambient temperatures andhumidity, the blend of (a) and a binding solution into a mixingapparatus to produce granules, wherein said binding solution compriseslignin-derived material and a mixture of polyols, which is incorporatedas an atomized solution; and f. recycling granules back into the mixingapparatus. 47-65. (canceled)
 66. The granule of claim 1, furthercomprising a bulk density material. 67-75. (canceled)